Hydrocarbon fuels



June 17, 1947. w. A. PRQELL. 422956355 HYDRocARBoN FUELS Filed March 27,1944 Patented June i?, :if

PATENT I OFFICE HYDROCARBON FUELS Wayne A. Proell, Chicago, Ill.,assignor to Standard Oil Company, Chicago, Ill., a corporation ofIndiana Application March 27, 1944, Serial N0. 528,234

12 Claims.

This invention relates to improvements in hydrocarbon fuels,particularly hydrocarbon fuels such as furnace or burner oils and fuelsfor compression-ignition internal combustion engines such as Dieselengines. More specifically the lnvention relates to hydrocarbon fuel oilcompositions which are substantially unsusceptible to filtercloggingland to the method of inhibiting the filter `clogging tendencyof such hydrocarbon fuels.

The requirements for acceptable fuels for oil burners and for Dieselengines include freedom from the tendency to clog filter screens and thenumerous iine passages and openings present in fuel oil burners and inDiesel engines. The fuel oil used in such equipment can interfere withthe performance of various parts in such equipment in several ways,among which are clogging, gumming, corrosion, etc. Particularlydetrimental to good performance are sediments, which may be of theso-called casual type or so-called noncasual type. Casual sedimentsinclude sand, dirt, iron rust, dust, water emulsions and miscellaneousdebris. The nature of casual sediment is such that its avoidance isentirely a problem of keeping the original oil clean and free of addeddirt, etc. The non-casual sediment is that sediment which may form in anoil during use. Such sediment is a hydrocarbon sediment originatingmainly in the oxidation and polymerization of all, or a portion of theoil. It is very finely divided as it forms and either clogs smallopenings and fine pores of the filters or it can coagulate into coarsersediment to form massive deposits which also clog larger openings in thefilter. It is responsible for the major part of so-cal-led sedimentdifliculties.

The tendency of fuels to clog lters varies with different fuels. Forexample, it has been observed that virgin fuels or fuels containing asubstantial amount of virgin stocks clog filters to a lesser degree thando fuels of crack stocks.

It is an object of the present invention to provide a hydrocarbon fuelhaving substantially nonclogging tendencies.

It is another object of the invention to provide a hydrocarbon fuelinhibited against the tendency to cause clogging.

Still another object of the invention is to provide a method ofinhibiting the clogging tendency of hydrocarbon fuels.

Other objects and advantages of the invention will become apparent fromthe following description thereof.

l have discovered that the foregoing objects can 55 be attained byadding to a hydrocarbon fuel oil, particularly those hydrocarbon fueloils which normally have a tendency to cause clogging of filters, smallopenings and the like, small amounts of a dispersing agent, preferablyan oil-soluble or oil-dispersable polyvalent metal soap in combinationwith small amounts of a metal deactivator such as, for example, thecondensation product of an aldehyde or a ketone with a primary amine.

The polyvalent metal soaps employed in the present invention arepreferably the heavy metal soaps of saturated and unsaturated aliphaticfatty acids, naphthenic a'cids, sulfonic acids and the like. Specificexamples of metal soaps which can be used in the present invention arealuminum oleate, aluminum naphthenate, aluminum sulfonate, aluminumstearate, iron oleate, iron naphthenate, zinc oleate, chromium oleate,chromium naphthenate, etc.

It has heretofore been observed that the tendency of organic substancesto oxidize in the presence of certain metals can be substantiallyreduced by adding to such organic substances certain compounds whichhave the property of rendering the metal inactive. Such compoundsexhibiting this property are commonly referred to as metal deactivatorsand the term metal deactivators as used herein,and in the appendedclaims mean those compounds which exhibit this metal deactivatingproperty.

Metal deactivators which can be suitably used in combination with themetal soaps of the foregoing type are condensation products obtaine1 bythe reacting of ortho hydroxy aromatic aldehydes or ketones such as2-hydroxybenzaldehyde, 2-4-dihydroxybenzaldehyde, Z-hydroxy-B-methoxybenzaldehyde, 2,2'-dihydroxybenzophenone, etc., with a primary amine,particularly a polyalkylene amine, containing at least three nitrogenatoms of which at least two are primary amino nitrogen atoms such as,for example, methyl diamine, ethylene diamine, diethylene triamlne, 1:10-decylene diamine, triethylene tetramine, propylene diamine,tetraethylene pentamine, NJW-dibeta amina ethylene piperazine; or thecondensation product obtained by reacting an aromatic, aliphaticalicyclic, or heterocyclic aldehyde or ketone such as crotonaldehyde,butyraldehyde, heptaldehyde, isobutyraldehyde, methyl hexyl ketone,furfural, acetaldehyde, acetophenone, benzaldehyde, acetone, vanilin,valeraldehyde, octyl aldehyde, cinnamaldehyde, hexone, diisobutyl ketoneand the like, with a primary amine, particularly a polyalkylene aminehaving at least 3 nitrogen atoms of which at least two are primary aminonitrogen atoms of the type above described. Other suitable metaldeactivators are the reaction products of an hydroxylamine with an orthohydroxy aromatic aldehyde or an ortho hydroxy aromatic ketone.

Examples of reaction products of the foregoing type are disalicylalethylene diamine, di(2hy -propylene diamine, fur

droxy-3-methoxybenzol) fura] triethylene tetramine, benzaldehydetetraethylene pentamine, disalicylal N,N'dlbeta amino ethyl piperazine,dihydroxy benzophenone dieth.

ylene triamine, tributyraldehyde triethylene tetramine, tetra diisobutylketones, tri-propylene tetramine, ortho hydroxybenzandoxime, orthohydroxy acetophenon-oxime and the like.

The clogging effect of fuel"oils can be determined in an apparatus ofthe type illustrated in the accompanying drawings in which:

Figure 1 is a diagramm tic illustration of an apparatus for 'determiningthe clogging time of hydrocarbon fuel oils; and

Figure 2 is an enlarged sectional view of the filter element of Figure1.

Referring to Figure 1, the oil Ain a container I, for example a barrelof about 50 gallon capacity, is maintained at a temperature of about 140F., as indicated by thermometer 2, by heating means, for example anelectric heater 3. The oil is then pumped through a pipe 4 extendinginto the container I substantially to the half-way mark, by means of asuitable punp 5, for example a standard oil burner pump having asediment bulb and a fine mesh screen (not shown), for separating out anycoarse casual sediment. A pressure gauge 6 is connected to the pump 5 bymeans of pipe 1 provided the pump is regulated bymea*is ef a by-passline 9 and by-pass regulator valve i0. Oil leaving the pump 5 passesthrough line II provided with a suitable pressure gauge such as aBourdon gauge I2, and passes The oil passes through the filter elementI3 and is returned to the container I through line I4 provided with avalve I5. The outlet pressure of pump 5 is regulated by passing the oilfrom the container I through the by-pass line 9 and regulating the flowtherethrough by means of valve II!- A sensitive Bourdon gauge measuresthe oil pressure immediately before the oil enters the filter and sincethe outlet line I4 is opened to the atmosphere and is unthrottled, thepressure indication on the Bourdon gauge is,equal to the pressure dropacross the filter element I3. The pressure drop across the lter elementI3 is kept constant and the flow therethrough measured by closing valveI5 in line I4 and by-passing the fuel oil through lines I6 and Il' andvalve I8, By withdrawing a portion of the fuel oil in this manner into agraduated container the rate of flow through the filter element I3 canbe measured and regulated to a constant iiow.

with a valve 8. The outlet pressure on through a filter element I3.

drawn through lines I6 and I1 for measuring the rate of flow is returnedto container I. In the event the filter becomes completely clogged,pressure on the system is released by means of safety valve I'Ia invalved line I6a.

Referring to Figure 2, the filter element I3 comprises a holder I9provided with a shoulder 20 on which rest gasket 2| and sintered copperfilter 22. Filter 22 is held against the shoulder 20 by means ofcompression spring 23 and threaded runner h coupled to the filterelement I3 by means of the threaded bushing 25 and line Il of the systemis connected to the outlet of the filter element I3 through threadedportion 26 of the holder I9.

In making a test a minimum oil sample of about 50 gallons is used tosecure ratio generally met with in practice. Before a test is made, theoil container is allowed to stand overnight to permit any coarse casualsediment to settle out. The oil used in the test maintained at atemperature of about F. is circulated through the filter element I3, andthe rate of flow and clogging time noted. l

taining 0.01% aluminum naphthenate and 0.002% salicylaldoxime(orthohydroxy benzaldoxime) were tested in the apparatus just describedand the following results obtained:

l Corrected to same initial flow rate.

The above data clearly demonstrate the eiectivenessof small amounts ofaluminum soap and a metal deactivator in increasing the clogging time ofa hydrocarbon fuel oil. Inasmuch as the filter element 22 is used inactual Diesel engines, and since fuel is circulated in actual Dieselengines, it is obvious that a similar improvement in fuel performancewould occur if the treated fuel were used in practice,

While the present invention has been described by reference to variousrepresentative compounds and has been illustrated by reference tospecific examples thereof, the invention is not to be limited to thevarious named compounds or to the specific examples but includes withinits scope such modifications as come within the spirit of the appendedclaims.

I claim:

1. A substantially non-clogging fuel oil composition comprising anormally liquid hydrocarbon fuel normally susceptible to cause cloggingcontaining in combination therewith from about 0.001% to about 0.1% ofan oil-soluble polyvalent metal soap and from about 0.005% to about0.05% of a condensation product selected from the class consisting of(1) the reaction product of a polyalkylene compound having at least 3amino nitrogen atoms, at least two of which are primary nitrogen atoms,with a carbonyl compound selected from the group consisting of aromaticaldehydes, aromatic ketones, aliphatic aldehydes, aliphatic ketones,alicyclic aldehydes, alicyclic ketones, heterocyclic aldehydgs, andheterocyclic ketones, and (2) the reaction product of an hydroxylamineand a phenolic-compound The 011 W'h- 75 selected from the groupconsisting of'ortho hy- 24. Line II of the system is.

the' high oil to surface droxy aromatic aldehydes and ortho hydroxyaromatic ketones.

2. A fuel oil composition as described in claim 1 in which thepolyvalent metal soap is an aluminum soap.

3. A fuel oil composition as described in claim 1 in which thepolyvalent metal soap is an iron soap.

4. A fuel oil composition as described in claim 1 in which thepolyvalent metal soap is a chromium soap.

5. A substantially non-clogging fuel oil composition comprising anormally liquid hydrocarbon fuel oil normally susceptible to causeclogging and in combination therewith from about 0.001% to about 0.1% ofa polyvalent metal soap and from about 0.005 to about 0.05% of thecondensation product obtained by reacting an aliphatic aldehyde with apolyalkylene amine having at least 3 amino nitrogen atoms, at least twob of which are primary nitrogen atoms;

6. A fuel' oil composition as described in claim 5 in which thepolyvalent metal soap is an aluminum soap and the condensation productis furfural triethylene tetramine.

7. A substantially non-clogging fuel oil composition comprising anormally liquid hydrocarbon fuel oil normally susceptible to causeclogging, from about 0.001% to about 0.1% of a polyvalent metal soap andfrom about 0.005% to about 0.05% of the condensation product of aphenolic compound selected from the class consisting of ortho hydroxyaromatic aldehydes and ortho hydroxy aromatic ketones with anhydroxylamine.

8. A fuel oil composition as described in claim '7 in which thepolyvalent metal soap is an aluminum soap and the condensation productis ortho hydroxy aryl aldoxime.

9. A fuel oil composition as described in claim 7 in which thepolyvalent metal soap is aluminum naphthenate and the condensationproduct is 2- hydroxy-benzaldoxime.

10. A substantially non-clogging fuel oil composition comprising anormally liquid hydrocarbon fuel oil normally susceptible to causeclogging and in combination therewith from about 6 0.001% to about 0.1%of aluminum naphthenate and from about 0.005% to about 0.05% of furfural`triethylene tetramine.

11. A substantially non-clogging fuel oil composition comprising anormally liquid hydrocarbon fue1 oil normally susceptible to causeclogging and in combination therewith from about 0.001% to about 0.1% ofiron naphthenate and from about 0.005% to about 0.05% of furfuraltriethylene tetramine.

12. In a system having. small passages subject to clogging in which anormally liquid hydrocarbon fucl oil normally having the tendency tocause clogging of said passages is employed, the method of substantiallyinhibiting such clogging Comprising employing in said system a normallyliquid hydrocarbon fuel oil normally susceptible to cause cloggingcontaining from about 0.001% to about 0.1% of a polyvalent metal soapand from about 0.005% to about 0,05% of a conden- 'sation productselected from the class consisting of (1) the reaction product of apolyalkylene compound having at least three amino nitrogen atoms, atleast two of which are primary nitrogen atoms, with a carbonyl compoundselected from the group consisting of aromatic aldehydes, aromaticletones, aliphatic aldehydes, aliphatic ketones, alicyclic aldehydes,alicyclic ketones, heterocyclic aldehydes, and heterocyclic ketones, and(2) the reaction product of a hydroxy amine and a phenolic compoundselected from the group consisting of ortho hydroxy aromatic aldehydesand ortho hydroxy aromatic ketones,

WAYNE A. PROELL.

REFERENCES CITED The following references are of record in the I le ofthis patent:

UNITED STATES PATENTS Number Name Date 2,301,795 Proell Nov. 10, 19422,338,500 Downing et al. (I) Jan. 4, 1944 2,181,121 Downing et al. (II)Nov. 28, 1939 2,351,339 White et a1. (I) Oct. 24, 1944 2,285,878 Whiteet al. (II) June 9, 1942 2,336,598 Downing et al. (III) Dec. 14, 1943

